Electron deficient metalloporphyrins containing aromatic rings in meso positions (1; R=C.sub.6 F.sub.5, X=F,Cl,Br, M=Fe) have been shown to be efficient catalysts for the highly selective air oxidation of light alkanes to alcohols (Ellis and Lyons, Cat. Lett., 3,389, 1989; Lyons and Ellis, Cat. Lett., 8,45, 1991; U.S. Pat. Nos. 4,900,871; 4,970,348), as well as for efficient decomposition of alkyl hydroperoxide (Lyons and Ellis, J. Catalysis, 141, 311, 1993; Lyons and Ellis, U.S. Pat. No. 5,120,886). They are prepared by co-condensation of pyrrole with the appropriate aldehyde (Badger, Jones and Leslett, "Porphyrins VII. The Synthesis of Porphyrins By the Rothemund Reaction", Aust.J.Chem., 17,1028-35, 1964 Lindsey and Wagner, "Investigation of the Synthesis of Ortho-Substituted Tetraphenylporphyrins", J.Inorg. Chem., 54,828, 1989; U.S. Pat. Nos. 4,970,348; 5,120,882), followed by metal insertion (Adler, Longo, Kampas and Kim, "On the preparation of metalloporphyrins", J.Inorg. Nucl.Chem., 32,2443,1970) and .beta.-halogenation; (U.S. Pat. Nos. 4,892,941; 4,970,348). ##STR1##
U.S. Pat. No. 4,892,941 discloses halogenated tetraphenyl porphyrins disclosed to be useful for oxidation of alkanes.
U.S. Pat. Nos. 4,895,680 and 4,895,682 disclose the use of azide and nitride transition metal ligands, i.e., coordination complexes, for the air oxidation of alkanes and other hydrocarbons.
U.S. Pat. No. 4,900,871 describes the use of iron halogenated coordination complexes for similar oxidations, disclosing that halogenating the coordination complex portion of the catalyst greatly increases the activity of the catalyst.
C. Chang and F. Ebina, J.Chem. Soc. Comm., 778 (1981) disclose fluorinating iron and manganese tetraphenyl-porphyrinato chloride catalysts to improve their stability in the oxidation of alkanes and alkenes using strong oxidizers such as iodosylbenzene.
The following references disclose the preparation of partially halogenated porphines.
M. J. Billig et al, Chem. Ind. (London), 654 (1969) disclose mesomonofluorodeuteroporphyrin-dimethyl ester, a porphyrin having one fluorine atom in a meso position and having --CH.sub.3 and --CH.sub.2 CH.sub.2 COOCH.sub.3 substituents in beta positions, the remaining beta positions being unsubstituted.
Y. Naruta et al, Tetr. Lett., 33, 1069 (1992) disclose 5,10,15,20-fluorooctaethylporphines, porphyrins having fluorine atoms at 1 to 4 of the meso positions and an ethyl group at each of the beta positions.
H. Onda et al, Tetr. Lett., 26, 4221 (1985) disclose 1,3,5,7-tetrafluoro-2,4,6,8-tetramethyl porphine, a porphyrin having no meso substituents and having a fluorine atom and a --CH.sub.3 group on each of the four pyrrole groups of the porphyrin.
A. Suzuki et al, Heterocycles, 33, 87 (1992) disclose 1-fluoro-2,4-diethyl-3,5,8-trimethyl-6,7-dimethoxycarbonylethylporphine, a porphyrin unsubstituted in meso positions and containing a fluorine atom in a beta position, along with ethyl, methyl and methoxycarbonylethyl groups, also in beta positions.
R. Bonnett et al, J.Chem. Soc. 1600 (1966) disclose 5,10,15,20-chlorooctaethylporphine, 5-chlorooctaethylporphine and 5,15-dichlorooctaethylporphine, compounds which contain 1 to 4 chlorine atoms in meso positions and octaethyl groups in beta positions.
Fischer et al, Chem.Ber., 46, 2460 (1913) disclose a porphyrin containing four chlorine atoms in meso positions and alkyl groups and carboxyalkyl groups in beta positions.
Fischer et al, Liebig's Ann.Chem., 494, 225 (1932) disclose 2,7,12,17-tetraethyl-5,10,15,20-tetrachloro-3,8,13,18-tetramethyl porphine, a porphyrin having four chlorine atoms in meso positions and alkyl groups in beta positions.
Gong et al, Can.J.Chem., 63, 406 (1985) disclose 5,10,15,20-tetrachlorooctaethylporphine and 5,10-dibromo-15,20-dinitrooctaethylporphine, compounds which contain four chlorine atoms and two bromine atoms, respectively, in meso positions, and eight ethyl groups in beta positions.
G. S. Marks et al, J.Am. Chem. Soc., 82, 3183 (1960) disclose 1,2,4-tribromo-3,5,8-trimethylporphin-6,7-dipropionic acid dimethyl ester, a porphyrin unsubstituted in meso positions and containing three bromine atoms in beta positions, as well as methyl groups and propionic acid dimethyl ester groups. The same authors disclose 2,4,8-tribromo-1,3,5-trimethylporphin-6,7-dipropionic acid dimethyl ester, in which the same substituents are situated at different locations on the ring.
J. S. Andrews et al, J.Am. Chem.Soc., 72, 491 (1950) disclose 1,4,5,8-tetramethyl-2,3,6,7-tetrabromoporphine, a porphyrin having four methyl groups and four bromine atoms distributed among the four pyrrole rings.
Fischer et al, Hoppe-Eysler's Z.Physiol.Chem., 191, 36 (1930) disclose 2,7-dibromo-3,8,12,13,17,18-hexamethylporphine, a porphyrin having two bromine atoms and six methyl groups in beta positions of the porphyrin ring.
L. R. Nudy et al, Tetrahedron, 40, 2359 (1984) disclose 5-bromoporphin, 5,15-dibromoporphin and 5,10,15-tribromoporphin, a beta-unsubstituted porphyrin having 1, 2 and 3 bromine atoms in meso positions.
G. F. Stephenson et al, J.Chem. Soc. 1600 (1966) disclose 5-bromooctaethylporphine, a porphyrin having one meso bromine atom, the other meso positions being unsubstituted, and eight ethyl groups in beta positions.
Fischer et al, Chem.Ber., 60, 1861 (1960) disclose 3,8-dibromodeuteroporphyrin-dimethyl ester, a meso-unsubstituted porphyrin having four methyl groups in beta positions, two bromine atoms in beta positions and two --CH.sub.2 CH.sub.2 COOCH.sub.3 groups in beta positions.
Goff et al, J.Am. Chem. Soc., 99, 3641 (1977) disclose Fe(II) (2,4-dibromodeuteroporphyrin dimethyl ester, a porphyrin having no meso eubstituents, and having two bromine atoms, three methyl groups and two CH.sub.2 CH.sub.2 COOOC.sub.3 groups in beta positions.